Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Rewritable phosphorescent paper by the control of competing kinetic and thermodynamic self-assembling events

Nature Materials volume 4, pages 546–549 (2005)Cite this article

Abstract

Security inks have become of increasing importance1,2. They are composed of invisible substances that provide printed images that are not able to be photocopied, and are readable only under special environments. Here we report a novel photoluminescent ink for rewritable media that dichroically emits phosphorescence due to a structural bistability of the self-assembled luminophor. Long-lasting images have been developed by using conventional thermal printers, which are readable only on exposure to ultraviolet light, and more importantly, are thermally erasable for rewriting. Although thermally rewritable printing media have already been developed using visible dyes3,4,5 and cholesteric liquid crystals6,7, security inks that allow rewriting of invisible printed images are unprecedented. We realized this unique feature by the control of kinetic and thermodynamic processes that compete with one another in the self-assembly of the luminophor. This strategy can provide an important step towards the next-generation security technology for information handling.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Self-assembly of dendritic Cu(I) pyrazolate complexes by Cu(I)–Cu(I) metallophilic interactions.
Figure 2: Thermal printing and erasing of a phosphorescent image on a PET paper coated with a polymer film containing self-assembled Cu[C18]L2pz.
Figure 3: Luminescence dichroism of self-assembled Cu[C18]L2pz.

Similar content being viewed by others

References

  1. Yousaf, M. & Lazzouni, M. Formulation of an invisible infrared printing ink. Dyes Pigments 27, 297–303 (1995).

    Article  CAS  Google Scholar 

  2. Phillips, R. W. & Bleikolm, A. F. Optical coatings for document security. Appl. Opt. 35, 5529–5534 (1996).

    Article  CAS  Google Scholar 

  3. Tsutsui, K., Yamaguchi, T. & Sato, K. Thermochromic properties of mixture systems of octadecylphosphonic acid and fluoran dye. Jpn J. Appl. Phys. 33, 5925–5928 (1994).

    Article  CAS  Google Scholar 

  4. Naito, K. Amorphous–crystal transition of organic dye assemblies: application to rewritable colour recording media. Appl. Phys. Lett. 67, 211–213 (1995).

    Article  CAS  Google Scholar 

  5. MacLaren, D. C. & White, M. A. Dye–developer interactions in the crystal violet lactone–lauryl gallate binary system: implications for thermochromism. J. Mater. Chem. 13, 1695–1700 (2003).

    Article  CAS  Google Scholar 

  6. Tamaoki, N., Parfenov, A. V., Masaki, A. & Matsuda, H. Rewritable full-colour recording on a thin solid film of a cholesteric low-molecular-weight compound. Adv. Mater. 9, 1102–1104 (1997).

    Article  CAS  Google Scholar 

  7. Tamaoki, N. Cholesteric liquid crystals for color information technology. Adv. Mater. 13, 1135–1147 (2001).

    Article  CAS  Google Scholar 

  8. Yam, V. W. -W. & Lo, K. K. -W. in Molecular and Supramolecular Photochemistry Vol. 4; Multimetallic and Macromolecular Inorganic Photochemistry (eds Ramamurthy, V. & Schanze, K. S.) Ch. 2, 31–112 (Marcel Dekker, New York, 1999).

    Google Scholar 

  9. Ford, P. C., Cariati, E. & Bourassa, J. Photoluminescence properties of multinuclear copper(I) compounds. Chem. Rev. 99, 3625–3647 (1999).

    Article  CAS  Google Scholar 

  10. Enomoto, M., Kishimura, A. & Aida, T. Coordination metallacycles of an achiral dendron self-assemble via metal-metal interaction to form luminescent superhelical fibers. J. Am. Chem. Soc. 123, 5608–5609 (2001).

    Article  CAS  Google Scholar 

  11. Kishimura, A., Yamashita, T. & Aida, T. Phosphorescent organogels via 'metallophilic' interactions for reversible RGB–colour switching. J. Am. Chem. Soc. 127, 179–183 (2005).

    Article  CAS  Google Scholar 

  12. Carvajal, M. A., Alvarez, S. & Novoa, J. J. The nature of intermolecular CuI···CuI interactions: A combined theoretical and structural database analysis. Chem. Eur. J. 10, 2117–2132 (2004).

    Article  CAS  Google Scholar 

  13. Pyykkö, P., Runeberg, N. & Mendizabal, F. Theory of the d10–d10 closed–shell attraction: 1. Dimers near equilibrium. Chem. Eur. J. 3, 1451–1457 (1997).

    Article  Google Scholar 

  14. Kim, S. J. et al. Trinuclear gold(I) pyrazolate complexes exhibiting hexagonal columnar mesophases with only three side chains. Chem. Mater. 10, 1889–1893 (1998).

    Article  CAS  Google Scholar 

  15. Barberá, J. et al. (Pyrazolato)gold complexes showing room–temperature columnar mesophases. Synthesis, properties, and structural characterization. Inorg. Chem. 37, 2960–2967 (1998).

    Article  Google Scholar 

  16. Kubas, G. J. Tetarakis(acetonitrile)copper(1+)hexafluorophosphate(1−). Inorg. Synth. 28, 68–70 (1990).

    CAS  Google Scholar 

Download references

Acknowledgements

We thank S. Harada (Ricoh Co) for fabrication of phosphorescent papers; T. Kato (The University of Tokyo) for DSC measurements. A. K. acknowledges the JSPS Young Scientist Fellowship.

Author information

Authors and Affiliations

  1. Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

    Akihiro Kishimura & Takuzo Aida

  2. Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, 278-8510, Chiba, Japan

    Takashi Yamashita

  3. Department of Pharmaceutical Technology, Laboratory of Analytical Chemistry, Faculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, Shido, Sanuki, 769-2193, Kagawa, Japan

    Kentaro Yamaguchi

  4. Aida Nanospace Project, Exploratory Research for Advanced Technology, Japan Science and Technology Agency (JST), 2-41 Aomi, Koto-ku, Tokyo, 135-0064, Japan

    Takuzo Aida

Authors
  1. Akihiro Kishimura
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Takashi Yamashita
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kentaro Yamaguchi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Takuzo Aida
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Takuzo Aida.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary information and figures (PDF 1175 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kishimura, A., Yamashita, T., Yamaguchi, K. et al. Rewritable phosphorescent paper by the control of competing kinetic and thermodynamic self-assembling events. Nature Mater 4, 546–549 (2005). https://doi.org/10.1038/nmat1401

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat1401

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing